N-(ortho-substituted benzene or naphthalene carboxamidoethyle)para-phenylene diamines as coupler-developers

ABSTRACT

Novel coupler developers for preparing color transfer images. Essentially the coupler developers contain a coupling moiety linked to a silver halide developing moiety.

United States Patent 11 1 Simon [4 1 Jan. 16, 1973 [54]N-(ORTHO-SUBSTITUTED BENZENE 158] Field of Search....260/559 S, 560, 570B, 562 K, OR NAPHTHALENE 260/57l,3l0A,558 A,559 A,518R,Sl9,CARBOXAMIDOETHYLE)PARA- 507 R PHENYLENE DIAMINES AS COUPLER- DEVELOPERS[56] References Cited [76] Inventor: Myron S. Simon, 25 David Road,UNITED STATES PATENTS Newm" Centre 02194 2,710,803 6/1955 Salininen eta1. ..260/3 10 A [22] Ffl d; J 9 1969 3,051,742 8/1962 Ehrhart et a1..260/562 K 3,297,758 I 1/1967 Hoeschele et a1. [21] Appl. No.: 847,7683,404,005 10/1968 Tobey 260/560 Related Application Primary Examiner-S.D. Winters [62] Division of Ser. No. 598,870, Dec. 2, 1966, Pat. No.Attorney-Brown and Mikulka, Stanley Mervis and 3,537,850. Alvin lsaacs[52] US. Cl'.... .....260/559 S, 260/559 A, 260/558 A, ABSTRACT 1: g lgK Novel coupler developers for preparing color transfer 260/570 26 I5 2I images. Essentially the coupler developers contain a [511 260/479260/207 260/2071 260/571 coupling moiety linked to a silver halidedeveloping moiety.

3 Claims, 1 Drawing Figure PATENTEDJAN 1 8 I973 3,71 1,546

SUPPORT PLER-DEVELOPER LVER HALIDE EMULSION NG composrnou E- RECEIVINGLAYE R SUPPORT INVENTQR.

fi/wwn Mm and ATTORNEYS N-(ORTHO-SUBSTITUTED BENZENE OR NAPHTHALENECARBOXAMHDOETHYLEWARA- PHENYLENE DIAMINES AS COUPLER- DEVELOPERS Thisapplication is a division of application Ser. No.

598,870 filed Dec. 2, 1966 now U. S. Pat. No. 3,537,850.

This invention relates to photography and, more particularly, to novelprocesses and products for preparing color transfer images.

A primary object of this invention, therefore, is to provide novelprocesses and products for preparing color images by diffusion transfer.

Another object is to provide novel photographic systems wherein anexposed light-sensitive silver halide emulsion is developed in thepresence of a compound which is both a color developer and a coupler,the developer moiety is selectively oxidized as a function ofdevelopment, the oxidized compound couples intermolecularly to form anon-diffusible reaction product of substantially higher molecularweight, while the unreacted compound is free to transfer by imbibitionto a superposed layer or stratum where it is oxidized and then couplesinter-molecularly to form a positive dye transfer image. I

Still another object is to provide novel compounds for use in theaforementioned systems.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the several steps and the relationand order of one or more of such steps with respect to each of theothers, and the products possessing the features, properties, and therelation of elements which are exemplified in the following detaileddisclosure, and the scope of the application of which will be indicatedin the claims.

For a fuller understanding of the nature and objects of the invention,reference should be had to the following detailed description taken inconjunction with'the accompanying drawing wherein:

The FIGURE is a partially schematic, partially enlarged fragmentarysectional view illustrating a previously exposed photographic product ofthis invention during processing, thereof.

The objectives of this invention are accomplished by providing novelprocesses and products utilizing a novel class of compounds whichcontain both a coupling moiety and a silver halide developing moiety,hereinafter referred to as coupler-developers." The coupling moiety isselected from the class of color couplers heretofore known to couplewith oxidized color developer, e.g., phenol, naphthol, aniline,naphthylamine or active methylene color couplers, etc., and thedeveloper moiety in turn is selected from the class of color developerswhich are heretofore known to provide an oxidation product which maycouple with color couplers of the foregoing description to form a dye,e.g., an indoaniline, indophenol, or an azomethine dye. The coupler anddeveloper moieties are so positioned in the molecule with respect to oneanother so as to preclude self-coupling or intramolecular couplingbetween the coupler moiety and oxidized developer moiety.

The coupler-developers of this invention may be represented by thefollowing formula:

wherein:

X represents a color coupler, e.g., a hydroxy-phenyl, a-hydroxynaphthyl,aminophenyl, oz-aminonaphthyl or methylene color coupler such asdescribed, for example, in Mees, The Theory of the Photographic Process,Revised Edition, 1954, pp. 594-604;

D represents an aromatic primary amino color developer moiety, e.g., ofthe p-aminophenol and pphenylenediamine series;

L is a divalent linking group linking the developer moiety, D, to thecoupler moiety, X; and

n is a positive integer from 1 to 2, the developer moiety, D, beingpositioned in the molecule with respect to the coupler moiety, X, so asto preclude selfcoupling. This may be effected in the following manner:

1. having the primary amino substituent of the developer moietyseparated from the coupling position of the coupler moiety by more thanfour or less than three other atoms so as to preclude self-coupling toform a fiveor sixmembered ring; or

2. in instances where the amino substituent is separated from thecoupling position by four atoms, the developer moiety is not linked tothe coupler in a position ortho-, or in the case of naphthyl couplers,perito the coupling position.

While the developer moiety may be the radical of a p-aminophenol colordeveloper, e.g.,

and the known substituted derivatives thereof, the preferred colordeveloper moieties are monovalent radicals of color developers of thep-phenylenediamine series. As examples of useful color developers ofthis class, mention'may be made of:

N,N-diethyl-p-phenylenediamine, 2,-amino-5-diethylamino toluene,N-ethyl-B-methanesulfonamido-ethyl-3-methyl-4- amino-aniline,4-amino-N-ethyl-3-methyl-N-(B-sulfoethyl)aniline,4-amino-N-ethyl-3-methoxy-N-(B-sulfoethyl)aniline,4-amino-N-ethyl-N-(B-hydroxyethyl)aniline,4-amino-N,N-diethyl-3-hydroxymethyl aniline,4-amino'N-methyl-N-(fl-carboxyethyl)anilinc,4-amino-N,N-bis(fi-hydroxycthyl)aniline,4-amino-N,N-bisUB-hydroxyethyl)-3-3-methyl aniline,3-acetamido-4-amino-N,N-bis(B-hydroxyethyl)aniline, 4-amino-N-ethyl-N-(2,3-dihydroxypropyl)-3- methylaniline sulfate salt,4-amino-N,N-diethyl-3-(3-hydroxypropoxy)aniline,

and the like. The color developer moiety may, for reasons to bediscussed hereinafter, be present as a Schiff base derivative.

The divalent linking radical, L, may be any of the linking radicalsheretofore disclosed in the art as useful to link a developing moiety toa dye moiety to provide a dye developer, i.e., a dye which is also asilver halide developing agent. Dye developers and the use thereof aredescribed and claimed, for example, in U. S. Pat. No. 2,983,606, issuedto Howard G. Rogers. Useful linking groups are disclosed in this patentand in particular are described and claimed in U. S. Pat. No. 3,255,001issued June 7, 1966 to Elkan R. Blout and Howard G. Rogers, as well asin other issued patents. Such linking groups include, by way of example,alkylene, phenylene, -alkylphenyl-, CO--, -CONH- alkyl-, etc.

As was mentioned previously, the coupling moiety may be selected fromany of the known couplers such as are described, for example, in theaforementioned Mees text. The preferred couplers are taken from theclasses of a-naphthol, phenol, aniline and anaphthylamine couplers,including substituted derivatives thereof. This preferred class may berepresented by the formula:

L, n and D have the meanings heretofore noted; Y is hydroxy oramino,e.g., a primary, secondary or tertiary amino substituent of the formulawherein each R may be hydrogen, a hydrocarbon radical, e.g., alkyl, suchas methyl, ethyl, butyl, dodecyl, etc., aryl such as phenyl or naphthylattached through a carbon atom thereof to the nitrogen atom, a cyclicalkyl such as cyclopentyl or cyclohexyl, i.e., where both Rs arealkylene comprising together with the nitrogen atom a heterocyclic ring,a substituted alkyl, such as hydroxyethyl, methoxyethoxyethyl,polyglycoloxyethyl, carboxymethyl, carboxyethyl, ethylcarboxymethyl,benzyl, phenylethyl, sulfo-phenylethyl, acetylaminophenylethyl,succinylamino, phenylethyl, furanemethyl, or a substituted aryl such asmethylphenyl, ethylphenyl, etc., couplers containing such substituentsbeing disclosed, for example, in U. S. Pat. No. 3,245,795, compoundswherein Y is hydroxy being the most preferred;

Z represents a coupling position para to the Y substituent and may behydrogen or any of the substituents heretofore known in the art (such asdisclosed in the aforementioned Mees text) which are replaceable byoxidized aromatic amino color developer in so-calledelimination-coupling reactions, e.g., chloro, bromo, carboxy, sulfo,hydroxy, alkoxy, hydroxyalkyl, etc.; and

A represents the atoms necessary to complete an aromatic ring of thebenzene or naphthalene series, which ring may be further substituted.

As in the coupler-developers of formula A, the developer moiety ispositioned so as to preclude intramolecular coupling of the oxidationproduct.

As examples of useful compounds within the scope 5 of Formulas A and/orB, mention may be made of:

In general, the novel compounds of this invention, that is, thecompounds of Formulas A and B, may be readily synthesized by appropriatereplacement or substitution reactions between a compound providing thecoupling moiety and a compound providing the color developer moiety. insome instances wherein the coupling moiety is a phenol or naphthol, itmay be desirable for the hydroxy substituent to be protected during thisreaction, e.g., by acylation. Following reaction, the protective groupmay be removed in known manner by hydrolysis. Since the generalreactions by which the present compounds may be prepared are in generalanalogous to the preparation of dye developers such as disclosed in theaforementioned patents and elsewhere in the patent literature, thepreparation of the present compounds will be readily apparent to thoseskilled in the art in the light of the present description, asexemplified by the following examples.

EXAMPLE 1 A mixture of 162.0 g. (1.34 M) of N-ethylaniline and 137.0 g.(0.67 M) of B-bromoethylamine hydrobromide was stirred for 105 minuteswhile the temperature was slowly raised to 145C. [At about l05l10C.there was some heat of reaction which sent the temperature briefly to140C.] The mixture was then maintained at 145C. with stirring for anadditional 2 hours, after which it was cooled overnight and then pouredinto 400 ml. of 10 percent sodium hydroxide. It was then heated on asteambath, cooled, and the resulting mixture was extracted with either.The ethereal solution was dried over sodium hydroxide pellets, filtered,the ether evaporated, and then distilled to yield 59.8 g. (54.5 percentyield) of:

N-ethyl-N-B-aminoethyl-aniline To a solution of 19.3 g. (0.084 M) of:

(II) oooom v COOH l-acetoxy-2-naphthoic acid in 175 ml. of acetone, 11.8ml. (0.84 M) of triethylamine were added. The mixture was cooled to 5C.and 11.5 g. (0.84 M) of isobutylchloroformate were added. After stirringfor about 25 minutes at 5 C., a solution of 14.5 g. (0.0885 M) ofN-ethyl-N-B- aminoethyl-aniline (l) in ml. of acetone was added. Theresulting mixture was removed from the cold bath and stirred overnightat room temperature while protecting from moisture. The acetone was thenevaporated in vacuo and the residue was treated with ice-water to yielda precipitate which was filtered, triturated with sodium bicarbonatesolution, filtered, and

then dried in vacuo over phosphorous pentoxide to yield a sticky solid.This solid was then titrated with hexane and filtered to provide 23.5 g.of a soupy white solid, m.p. 1021 10C. dec. This solid was crystallizedfrom 300 ml. of toluene to yield 13 g. (40 percent yield) of agelatinous white precipitate, m.p. 129-131 C., of the formula:

(III) )0 0 on,

A solution of 5.82 g. (0.0252 M) of sodium sulfanilate dihydrate in 30ml. of water was cooled to 15C. A solution of 1.76 g. (0.0252 M) ofsodium nitrite in water was added and the resulting mixture wasimmediately poured into 5.1 ml. of concentrated BC] in 30 g. of ice.After allowing it tostand for about 20 minutes, the mixture was thenpoured into a chilled solution containing 9 g. (0.024 M) of the amide(III) in ml. of methyl cellosolve plus 60 ml. of 3N HCl. The resultingpink mixture was stirred in the cold for 2% hours and refrigeratedovernight. It was then deaerated with a stream of nitrogen and keptunder a blanket of nitrogen while ml. of 3N sodium hydroxide were added.The reaction solution was then stirred at room temperature for 30minutes, after which period it was neutralized with 25 ml. of aceticacid. l-lCl was added and the resulting dark gum was filtered off anddried in vacuo over phosphorous pentoxide and potassium hydroxide toyield 12 g. of a dark solid. This solid was further purified bydissolution in 500 ml. of hot water, filtering, and acidifying withdilute HCl to yield a precipitate which was filtered and dried to yield9.2 g. ofa maroon solid, m.p. 200C. dec. with prior sintering. Forfurther purification, 7.4 g. of the solid were stirred with 50 ml. of 3Nsodium bicarbonate and 50 ml. of water for 30 minutes, filtered andacidified with 55 m1. of 3N HCl to yield a precipitate which wasfiltered and dried in vacuo over phosphorous pentoxide to yield 7.3 g.ofa red azo dye, m.p. 200205C., of the formula:

A solution was made under nitrogen, of 7.2 g. of this dye (W), ml. ofwater and 30 ml. of 3N sodium hydroxide. This solution was introducedinto a Parr hydrogenator and reduced with hydrogen over 2 g. ofpalladium/barium sulfate. Hydrogen uptake was complete in 25 minuted toyield a colorless solution which was acidified with 50 ml. of 3N HCl,and catalyst and occluded sulfanilic acid were filtered off. Thefiltrate was treated with aqueous acetic acid to a pH of about 4 tocause precipitation. Filtration, followed by drying in vacuooverphosphorous pentoxide yielded a yellow solid. Isolation was effected bysolution in 15 ml. of warm acetic acid and filtration followed byaddition of 15 ml. of acetic acid saturated with HCl then 150 ml. of dryether, to yield a light-colored precipitate. This precipitate wasfiltered through a sintered glass filter and then transferred quickly toa desiccator where it was dried in vacuo over phosphorous pentoxide toyield 2.5 g. of the amino hydrochloride of the couplerdeveloper ofFormula 1, a light colored solid, m.p. l-150C. dec.

EXAMPLEZ A mixture of 10.4 g. of acetylsalicylic acid in 122 cc. ofacetone and 8.14 cc. of triethylamine was cooled with stirring to -5C.7.94 g. of isobutylchloroformate were then added to yield a whiteprecipitate. After stirring at 5C. for about 25 minutes, a solution ofg. of N-ethyl-N-,8-aminoethyl-aniline (l) in 10 cc. of acetone wasadded. The reaction mixture was then removed from the cold bath, stirredovernight at room temperature, the acetone evaporated in vacuo, and coldwater was added to the residue. The liquid phase was then decanted toprovide a pasty product. This was purified by trituration with a smallamount of ether,

with water, and with sodium bicarbonate solution, washed with water andthen dried in vacuo over phosphorous pentoxide to yield a white solid,m.p. about 70C. This white solid was recrystallized from 250 cc. ofligroin and 50 cc. of toluene to yield 10 g. (50.3 percent yield) of awhite crystal amide, m.p. 89-91C., having the following formula:

3.24 g. of 2,5-dich1oroani1ine were dissolved in a boiling solution of 8cc. of cone. HCl and 35 cc. of water.

The solution was cooled in an ice bath to about 10C. at whichtemperature crystallization occurred. A cold solution of 1.39 g. ofsodium nitrite in 3 cc. of water was added dropwise. The mixture wasstirred for 10 minutes and filtered in the cold to provide a pale yellowsolution. The solution was added slowly in the cold to a stirredsolution of 6.52 g. of the amide (V) in 42 cc. of 3N HCl. The resultingmixture turned deep red and a precipitate started to form. The mixturewas stirred at 0 to 5C. for about 2% hours and then filtered. Over- Inight more solid precipitated from the mother liquor and the solids werecombined, the combined solids being:

, 8 v1 ooocrn The acetylated azo dye (VI) was added to cc. of previouslydeaerated 3N sodium hydroxide solution. After stirring for 2 hours untilalmost complete solution occurred, 100 cc. of 3N HCl were added dropwisewhile stirring vigorously to yield an orange precipitate which wasfiltered, washed with water, dried in air and recrystallized from about100 cc. of benzene and 25 cc. of hexane to yield a product, m.p.l43-146C. This product was recrystallized once more from ethanol toyield 8.0 g. (86.6 percent yield) of the azo dye, m.p. l49l 5 1C.,having the formula:

W1 HI I 7.5 g. of the azo dye (VIl) were dissolved in about cc. ofboiling ethanol, the solution cooled to about 40-45C. (some of the dyecrystallized out) and l g. of palladium/barium sulfate (10 percent) wasadded, then 1.37 cc. of cone. HCl. The dye was reduced in a Parrhydrogenator for about one hour and the catalyst was then filtered off.The ethanol was evaporated to about 15 cc. and a large excess of etherwas added. The ether was stirred with a glass rod while heating on asteambath to yield a fine beige powder. This powder was dissolved inabout 60 cc. of methanol on a steambath, filtered and rapidlyreprecipitated with ether. It was then left in a refrigerator for about2 hours and filtered to yield 1.2 g. of the coupler-developer of formula2, as the dihydrochloride, a light beige powder, m.p. 229-231C.

This coupler-developer was also prepared from the acetylated amide (V1)by nitrosation and reduction of the nitroso group.

As was stated previously, the coupler-developers of this inventionprovide an oxidation product which can couple inter-molecularly, butwhich will not self-couple or couple intra-molecularly. When twomolecules so couple, a dye of substantially. higher molecular weight isformed. it will be apparent that three or more molecules of oxidizedcoupler-developer may couple to provide a polymeric dye of still highermolecular weight. In any event, the coupling of two or more moleculesprovides a dye which is relatively non-diffusible in the processingfluid.

With reference to the coupler-developer of Formula 1, the reactionmechanism upon which non-diffusible dye formation is predicated may beillustrated as follows:

CzHy,

Following oxidation, e.g., by development of an exposed silver halideemulsion, the nitrogen atom [bearing the free valence] of one moleculeof oxidized coupler-developer couples para to the naphtholic hydroxylgroup of another molecule to form a dye. Further intermolecular couplingof other molecules of oxidized coupler-developer may occur to provide apolymeric dye of greater molecular weight.

The novel coupler-developer of this invention may be employed in variousphotographic systems wherein color transfer image is predicated upon animagewise differential in mobility or diffusibility obtained as afunction of developing an exposed light-sensitive silver halideemulsion. Such a system is illustrated in the drawing.

As shown therein, a photosensitive element comprising a support 10having a layer 12 of coupler-developer and a light-sensitive silverhalide emulsion layer 14 which has been previously exposed to contain adevelopable image, is developed by spreading an aqueous alkalineprocessing composition 16 between the thus exposed element and asuperposed image-receiving element comprising an image-receiving layeror dyeable stratum 18 on a suitable support 20. The processingcomposition permeates emulsion layer 14 to layer 12 where at least aportion of the couplerdeveloper in layer 12 is dissolved in theprocessing medium. [if the particular coupler-developer employed is notreadily soluble in water, at least at the processing temperatureemployed, a suitable water-miscible organic solvent therefor may becontained in the processing composition.] The processing compositioncontaining coupler-developer thus formed thereafter contacts theemulsion layer where the developing moiety reduces exposed silver halideto image silver and as a function thereof is in turn oxidized. Thisoxidized developer then couples intermolecularly in the mannerpreviously described to form a dye in terms of exposed areas. This dyeis relatively non-diffusible in the processing medium and hence remainsin the photosensitive element. in unexposed areas, an imagewisedistribution of unoxidized and diffusible coupler-developer remains.This latter imagewise distribution is transferred at least in part, byimbibition, to the superposed image-receiving layer or dyeable stratumto form thereon in terms of unexposed areas of the emulsion an imagewisedistribution of couplerdeveloper. This imagewise distribution ofunoxidized coupler-developer may then be oxidized to form a positive dyetransfer image. The oxidation may be effected simply by exposure to air,e.g., upon separation of the respective elements following development,or, if desired, the receiving layer may contain an oxidizing agent tofacilitate oxidation and subsequent dye formation.

In the color transfer process just described, it will be appreciatedthat a negative color image is formed in the photosensitive element. Ifdesired the photosensitive element may be treated for removal of silverin conventional manner, e.g. by bleaching and subsequent fixation toprovide a useful negative image. Any residual coupler-developerremaining in unexposed areas may also be removed by conventionaltechniques to provide clean highlight areas in the negative image. Thisaspect of the invention may be employed, for example, as a system formaking positive reproductions from a negative, e.g., from a negative orreversed color transparency. Hence, as used herein, the terms positiveand negative" are given their ordinary meaning in the art and areintended to connote whether or not the image is a reverse image of thesubject matter to which the novel film unit of this invention isexposed.

Either or both of supports 14 and 20 may be transparent or opaque,depending upon whether reflection prints or transparencies arecontemplated. They may also be translucent or contain a translucentlayer so that the resulting image may be viewed either by reflected orby transmitted light to provide a single image which is both areflection print and a transparency. As examples of typical materialswhich may be employed for the respective supports, mention may be madeof films of cellulose acetate, cellulose nitrate, polyvinyl acetal,polystyrene, polyethylene terephthalate, polyethylene, polypropylene,etc., paper, glass and others. As an example of a particularly usefulmaterial for preparing a translucent layer, mention may be made oftitanium dioxide.

Layer 12 containing the coupler-developer may be prepared by applying tosupport 14 a coating containing the coupler-developer and a suitablepolymeric matrix or carrier, e.g., cellulose acetate hydrogen phthalate,gelatin, etc.

Emulsion layer 14 may comprise any of the conventional silver halideemulsions, e.g., silver chloride, silver bromide, silver bromiodide,silver chlorobromide or silver chlorobromoiodide. The emulsion layer mayalso contain the various additives heretofore employed in such layers,e.g., optical sensitizers, antifoggants, hardeners, plasticizers,coating aids, speed-increasing materials, ultraviolet absorbers, etc.The dispersing agent or substrate for the silver halide may be gelatinor some other colloidal material.

Image-receiving layer 18 may be any of those heretofore known in theart, e.g., a copolymer of vinylacetatc and vinyl alcohol, nylon,polyvinyl alcohol, gelatin, etc. and it may also include a suitable dyemordant such as poly-4-pyridine.

The developing composition comprises at least an aqueous solution of analkaline material such as sodium or potassium hydroxide. As wasmentioned previously, it may also contain a suitable water-miscibleorganic solvent for the coupler-developer, e.g., phenethyl alcoho]. inaddition, the processing composition may also contain other reagentsperforming specific desired,

functions, e.g., a viscous film-forming reagent such as hydroxyethylcellulose, sodium carboxymethyl cellulose, etc. it is to be understoodthat any of these ingredients may be present initially in the film unit,in which case the processing composition containing the desiredingredients is formed during processing by contacting the film unit withthe aqueous medium therefor. In any event, the processing compositionmay, if desired, be confined in a frangible container or pod such asdescribed, for example, in U. S. Pat. Nos. 2,543,181 and 2,634,886,issued to Edwin H. Land.

While for purposes of illustration, the couplerdeveloper has been shownin the drawing as being in a separate layer in the photosensitiveelement, it may also be contained in the same layer as the silver halideemulsion. When present in the same layer, it may be advantageous to useforms that have substantial stability in photographic emulsions. Forexample, it may be desirable to have theprimary amino developing moietypresent in the emulsion as a Schiff base derivative. Such Schiff basesmay be prepared by reacting primary amino developing agents withsulfonated, hydroxylated or carboxylated aromatic aldehydes of thebenzene or naphthalene series. A typical Schiff base color developingagent can be prepared by reacting a color developer moiety, e.g.,2-amino-5-diethylaminotoluene, and osulfobenzaldehyde. As is known, theSchiff base derivatives are activated upon contact with the aqueousalkaline composition.

Other variations in procedure or in the arrangement of elements will beapparent in the light of the foregoing description.

The following example shows by way of illustration and not by way oflimitation the practice of this invention.

EXAMPLE 3 A photosensitive element was prepared by coating a gelatinsubcoated film base at a speed of feet/minute with a solution comprising0.125 g. of the couplerdeveloper of Formula 1 dissolved in 5 cc. of4%cellulose acetate hydrogen phthalate in acetone. After this coatingdried, a blue-sensitive silver iodobromide emulsion was coated on at aspeed of 5 feet/minute and allowed to dry. This photosensitive elementwas exposed for 2 seconds and then developed by spreading between thethus exposed photosensitive element and a superposed image receivingelement at a gap of 0.0026 inch an aqueous processing compositioncomprising the following proportions of ingredients:

Water lO0.0 cc. Hydroxyethyl cellulose 4.5 g. Sodium hydroxide L5 g.Sodium carbonate 5.0 g. Phenethyl alcohol I 1.5 cc.

The image-receiving element was comprised of a 50:50 copolymer ofvinylacetate-vinyl alcohol containing 0.6 percent benzoyl peroxide on anitrate-subcoated sheet. After an imbibition time of approximately 1minute, the. image-receiving element was separated and contained apositive green-blue image.

The present invention makes it possible to obtain color transfer imagesof excellent quality and stability. The oxidative coupling in thephotosensitive element as a function of development forms anon-diffusible reaction product so that transfer thereof is effectivelyprecluded. This inability of unwanted dye to transfer makes it possibleto obtain transfer images having minimal stain and exhibitingexceptionally clean highlight areas. Further, the polymeric nature ofthe dye makes it possible to obtain a dye image having exceptionalstability to light, heat and other degradative forces.

While the preparation of a monochromatic image has been described in theillustrative example, it will be appreciated that the invention isadaptable to the preparation of multicolor images. Systems for preparingmulticolor images would, for example, employ multilayer photosensitiveelements comprising at least two appropriately sensitized emulsionlayers each having a suitable coupler-developer associated therewith.

it is also contemplated that a mixture of couplerdevelopers may beemployed in a single emulsion system to provide a useful black-and-whiteprocess. Hence, as used throughout the specification and claims, theterm color is intended to include the use of a black dye or a mixture ofdyes to provide a black image.

Since certain changes may be made in the above product and processwithout departing from the scope of the invention herein involved, it isintended that all matter contained in the above description or shown inthe accompanying drawing shall be interpreted as illustrative and not ina limiting sense.

What is claimed is:

l. compound of the formula:

COHH (CHz)2III- ZH5 NH: O!

ooNmomt-tg-oml NHz where Y is OH or NH and Z represents a couplingposition para to said Y substituent, said Z substituent being selectedfrom the group consisting of hydrogen, chloro, bromo, carboxy, sulfo andhydroxy.

2. A compound of claim 1 of the formula:

3. A compound of claim 1 of the formula:

2. A compound of claim 1 of the formula:
 3. A compound of claim 1 of theformula: